By Authority Of THE UNITED STATES OF AMERICA Legally Binding Document

Transcription

1 By Authority Of THE UNITED STATES OF AMERICA Legally Binding Document By the Authority Vested By Part 5 of the United States Code 552(a) and Part 1 of the Code of Regulations 51 the attached document has been duly INCORPORATED BY REFERENCE and shall be considered legally binding upon all citizens and residents of the United States of America. HEED THIS NOTICE: Criminal penalties may apply for noncompliance. e Document Name: HACH 8000: Using Reactor Digestion Method CFR Section(s): 40 CFR 136.3(a) Standards Body: Hach Chemical Company Official Incorporator: THE EXECUTIVE DIRECTOR OFFICE OF THE FEDERAL REGISTER WASHINGTON, D.C.

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3 Oxygen, COD, MR, 8000 USEPA 1 Reactor Digestion Method to mg/l COD (ULR); 3 to 150 mg/l COD (LR); 20 to 1500 mg/l COD (HR); 200 to 15,000 mg/l COD (HR Plus) DOC Method 8000 Scope and Application: For water, wastewater; digestion is required 1 Ranges 3 to 150 mg/l COD and 20 to 1500 mg/l COD are USEPA approved for wastewater analyses (Standard Method 5220 D), Federal Register, April 21, 1980, 45(78), Jirka, A.M.; Carter, M.J., Analytical Chemistry, 1975, 47(8), The ULR range is not available on the DR 2700 or the DR/2400. Test preparation How to use instrument-specific information The Instrument-specific information table displays requirements that may vary between instruments. To use this table, select an instrument then read across to find the corresponding information required to perform this test Table 1 Instrument-specific information Instrument DR 3900 DR 3800, DR 2800 Light shield LZV849 LZV646 Before starting the test: DR 3900, DR 3800, DR 2800 and DR 2700: Install the light shield in Cell Compartment #2 before performing this test. Some of the chemicals and apparatus used in this procedure may be hazardous to the health and safety of the user if inappropriately handled or accidentally misused. Please read all warnings and associated MSDS sheets. Run one blank with each set of samples. Run all tests (the samples and the blank) with the same lot of vials. The lot number appears on the container label. See Blanks for colorimetric determination. Spilled reagent will affect test accuracy and is hazardous to skin and other materials. Be prepared to wash spills with running water. Wear appropriate eye protection and clothing for adequate user protection. If contact occurs, flush the affected area with running water. Review and follow reagent MSDS safety instructions carefully. Store unused (light sensitive) vials in a closed box. If high chloride samples are being tested, refer to the Alternate reagents section. Page 1 of 12

4 Collect the following items: Description Quantity Beaker, 250-mL 1 Blender 1 COD Digestion Reagent vials varies DRB200 Reactor 1 Light Shield or adapter (see Instrument-specific information) 1 Magnetic stirrer and stir bar 1 Opaque shipping container for storage of unused, light-sensitive reagent vials varies Pipet, TenSette, 0.1 to 1.0 ml, with tips (for ,000 mg/l range) 1 Pipet, volumetric, 2.00 ml 2 Pipet Filler, safety bulb 1 Test Tube Rack 2 See Consumables and replacement items for reorder information. Reactor digestion procedure 1. Homogenize 100 ml of sample for 30 seconds in a blender. For samples containing large amounts of solids, increase the homogenization time. If the sample does not contain suspended solids, omit steps 1 and For the ,000 mg/l range or to improve accuracy and reproducibility of the other ranges, pour the homogenized sample into a 250-mL beaker and gently stir with a magnetic stir plate. 3. Turn on the DRB200 Reactor. Preheat to 150 C. See the DRB200 User Manual for selecting preprogrammed temperature applications. 4. Remove the caps from two COD Digestion Reagent Vials. (Be sure to use vials for the appropriate range.) Page 2 of 12

5 Reactor digestion procedure (continued) 5. Prepared Sample: Hold one vial at a 45-degree angle. Use a clean volumetric pipet to add 2.00 ml of sample to the vial. 6. Blank Preparation: Hold a second vial at a 45-degree angle. Use a clean volumetric pipet to add 2.00 ml of deionized water to the vial. 7. Cap the vials tightly. Rinse them with water and wipe with a clean paper towel. 8. Hold the vials by the cap over a sink. Invert gently several times to mix. The sample vials become very hot during mixing. For the ,000 mg/l vials: Use a TenSette Pipet to add 0.20 ml of sample to the vial. For the ,000 mg/l vials: Use a TenSette Pipet to add 0.20 ml of deionized water to the vial. Insert the vials in the preheated DRB200 Reactor. Close the protective lid. 9. Heat the vials for two hours. 10. Turn the reactor off. Before removing the vials, wait about 20 minutes for the vials to cool to 120 C or less. 11. Invert each vial several times while still warm. 12. Place the vials into a rack and cool to room temperature. Proceed to Colorimetric determination. Page 3 of 12

6 Colorimetric determination Stored Programs 431 COD ULR 430 COD LR 435 COD HR Zero Start 1. Select the test. Insert an adapter or light shield if required (see Instrument-specific information). Refer to the user manual for orientation. 2. Clean the outside of the vials with a damp towel followed by a dry one. 3. Insert the blank into the 16-mm cell holder. 4. ZERO the instrument. The display will show: 0 mg/l COD or 0.0 mg/l COD Read 5. Insert the sample vial into the 16-mm. 6. READ the results in mg/l COD. 7. If using High Range Plus COD Digestion Reagent Vials, multiply the result by 10. For most accurate results with samples near 1500 or 15,000 mg/l COD, repeat the analysis with a diluted sample. Blanks for colorimetric determination The blank may be used repeatedly for measurements using the same lot of vials. Store the blank in the dark. 1. Monitor decomposition by measuring the absorbance at the appropriate wavelength. Refer to the Range-specific test wavelengths table. 2. Zero the instrument in the absorbance mode. Use a vial containing 5 ml of deionized water and measure the absorbance of the blank. Record the value. 3. Prepare a new blank when the absorbance has changed by about 0.01 absorbance units. Page 4 of 12

7 Interferences Vial range Ultra Low Range 1 ( mg/l) Low Range (3 150 mg/l) High Range ( mg/l) High Range Plus (200 15,000 mg/l) Chloride is the primary interference when determining COD concentration. Each COD vial contains mercuric sulfate that will eliminate chloride interference up to the level specified in Column 1 of the Interfering substances table. Dilute samples with higher chloride concentrations. Dilute the sample enough to reduce the chloride concentration to the level given in Column 2. Note: For best results, use the low range and ultra-low range test for samples with high chloride concentrations (approaching maximum concentration) and low COD concentrations. If sample dilution will cause the COD concentration to be too low for accurate determination, add 0.50 g of mercuric sulfate (HgSO 4 ) to each COD vial before the sample is added. The additional mercuric sulfate will raise the maximum chloride concentration allowable to the level given in Column 3. 1 Ultra Low Range is not available on the DR Sample collection, preservation and storage Collect samples in glass bottles. Table 2 Interfering substances Column 1 (Maximum chloride concentration ) Use plastic bottles only if they are known to be free of organic contamination. Test biologically active samples as soon as possible. Homogenize samples containing solids to assure representative samples. Samples treated with sulfuric acid * to a ph of less than 2 (about 2 ml per liter) and refrigerated at 4 C can be stored up to 28 days. Correct the test results for volume additions. Column 2 (Suggested chloride concentration for diluted samples) Column 3 (Maximum chloride concentration with mercuric sulfate) N/A ,000 10,000 40,000 * See Optional reagents and apparatus. Page 5 of 12

8 Accuracy check Standard solution method Note: Refer to the instrument user manual for specific software navigation instructions. Required for accuracy check: 1000 mg/l COD Standard Solution OR Potassium acid phthalate (KHP), dried overnight at 120 C Deionized water, organic free Class A volumetric flasks Class A volumetric pipet 0.7 to 40.0 mg/l range 1. Prepare a 30-mg/L COD standard solution as follows: a. Pipet 3.00 ml of the 1000 mg/l standard into a 100-mL volumetric flask. b. Dilute to volume with deionized water and mix well. 2. Use 2 ml of the 30 mg/l COD solution in place of the sample. Follow the Colorimetric determination test procedure. The result should be 30 mg/l. Refer to the Standard adjust instructions in this procedure to adjust the curve with the reading obtained from the standard. 3 to 150 mg/l range 1. Prepare a 100-mg/L COD standard solution as follows: a. Pipet 10 ml of the 1000 mg/l standard into a 100-mL volumetric flask. b. Dilute to volume with deionized water and mix well. 2. Use 2 ml of the 100-mg/L solution in place of the sample. Follow the Colorimetric determination test procedure. The result should be 100 mg/l. Refer to the Standard adjust instructions in this procedure to adjust the curve with the reading obtained from the standard 20 to 1500 mg/l range Use 2 ml of 300 mg/l, 800 or 1000 mg/l COD standards for accuracy check. Page 6 of 12

9 200 to 15,000 mg/l range 1. Prepare a 10,000-mg/L COD standard solution as follows: a. Dissolve g of dried KHP in 1000-mL of organic-free deionized water. 2. Use 0.2 ml of the 10,000 mg/l COD solution in place of the sample. Follow the Colorimetric determination test procedure. The result should be 10,000 mg/l (after multiplying by 10). Refer to the Standard adjust instructions in this procedure to adjust the curve with the reading obtained from the standard. Standard adjust Alternate reagents 1. To adjust the calibration curve using the reading obtained with the standard solution, navigate to Standard Adjust in the software: OPTIONS>MORE>STANDARD ADJUST. 2. Turn on the Standard Adjust feature and accept the displayed concentration. If an alternate concentration is used, enter the concentration and adjust the curve to that value. Mercury-free COD2 Reagents can provide a mercury-free testing option for non-reporting purposes. For process control applications, COD2 Reagents will eliminate mercury waste and save on disposal costs. These reagents are fully compatible with test procedures and calibration curves programmed into the spectrophotometer. Determine chloride and ammonia for accurate results. Important Note: COD2 reagents are not approved for USEPA reporting purposes. Because COD2 reagents do not contain mercury as a masking agent, they exhibit a positive interference from chloride. Request a copy of the COD2 Reagent Vial Information Brochure, Lit. No. 1356, for more information about specific applications. Page 7 of 12

10 Method performance Program 430 (Range, mg/l) 431 (Range, mg/l) 435 (Range, mg/l) 435 (Range, ,000 mg/l) Standard 80 mg/l COD (Low Range) 30 mg/l COD (Ultra Low Range) 800 mg/l COD (High Range) 8000 mg/l COD (High Range Plus) Precision 95% Confidence Limits of Distribution Sensitivity Concentration change per Abs change mg/l COD 3 mg/l COD mg/l COD 0.5 mg/l COD mg/l COD 23 mg/l COD mg/l COD 230 mg/l COD Summary of method Range in mg/l COD 0.7 to 40.0 mg/l 1 1 Not available on the DR 2700 The results in mg/l COD are defined as the milligrams of O 2 consumed per liter of sample under the conditions of this procedure. The sample is heated for two hours with sulfuric acid and a strong oxidizing agent, potassium dichromate. Oxidizable organic compounds react, reducing the dichromate ion (Cr 2 O 7 2 ) to green chromic ion (Cr 3+ ). When the or the mg/l colorimetric method is used, the amount of Cr 6+ remaining is determined. When the mg/l or ,000 mg/l colorimetric method is used, the amount of Cr 3+ produced is determined. The COD reagent also contains silver and mercury ions. Silver is a catalyst, and mercury is used to complex chloride interferences. Test results are measured at the wavelengths specified in the Range-specific test wavelengths table. Table 3 Range-specific test wavelengths Wavelength 350 nm 3 to 150 mg/l 420 nm 20 to nm 2000 to 15,000 mg/l 620 nm Page 8 of 12

11 Consumables and replacement items Required reagents Description Quantity/Test Unit Catalog number Select the appropriate COD Digestion Reagent Vial: Ultra Low Range, 0.7 to 40 mg/l COD 1 2 vials 25/pkg Low Range, 3 to 150 mg/l COD 1 2 vials 25/pkg High Range, 20 to 1500 mg/l COD 1 2 vials 25/pkg High Range Plus, 200 to 15,000 mg/l COD 1 2 vials 25/pkg Water, deionized varies 4 L Alternate reagents 1 Description Quantity/Test Unit Catalog number Select the appropriate COD Digestion Reagent Vial: COD2, Low Range, 0 to 150 mg/l COD 1 2 vials 25/pkg COD2, High Range, 0 to 1500 mg/l COD 1 2 vials 25/pkg COD2, High Range, 0 to 1500 mg/l COD 1 2 vials 150/pkg COD2, High Range Plus, 0 to 15,000 mg/l COD 1 2 vials 25/pkg COD Digestion Reagent Vials, 3 to 150 mg/l COD 1 2 vials 150/pkg COD Digestion Reagent Vials, 200 to 1500 mg/l COD 1 2 vials 150/pkg COD Digestion Reagent Vials, ULR mg/l 1-2 vials 150/pkg COD Digestion Reagent Vials, HR plus,200-25,000 mg/l 1-2 vials 150/pkg These reagents are not approved for USEPA reporting purposes. Request a copy of the COD2 Reagent Vial Information Brochure, Lit. No. 1356, for more information about specific applications. Required apparatus Description Quantity Unit Catalog number Blender, 2-speed, 120 VAC 1 each OR Blender, 2-speed, 240 VAC 1 each DRB200 Reactor, 110 V, 15 x 16 mm 1 each LTV OR DRB200 Reactor, 220 V, 15 x 16 mm 1 each LTV Pipet Filler, safety bulb 1 each Pipet, Volumetric, Class A, 2.00 ml 1 each Page 9 of 12

12 Recommended standards and apparatus Description Unit Catalog number Beaker, 250-mL each 50046H COD Standard Solution, 300-mg/L 200 ml COD Standard Solution, 300-mg/L 500mL COD Standard Solution, 800-mg/L 200 ml COD Standard Solution, 1000-mg/L 200 ml Oxygen Demand Standard (BOD, COD, TOC), 10-mL ampules 16/pkg Pipet, TenSette, 0.1 to 1.0 ml each Pipet Tips, for TenSette Pipet /pkg Pipet Tips, for TenSette Pipet /pkg Potassium Acid Phthalate, ACS 500 g Stir Bar, 28.6 x 7.9 mm each Stirrer, Electromagnetic, 120 VAC, with electrode stand each Stirrer, Electromagnetic, 230 VAC, with electrode stand each Test Tube Rack, 16 mm each Wipes, Disposable 70/pkg Optional reagents and apparatus Description Unit Catalog number Balance, analytical, 80 g capacity, 115 VAC each Flask, volumetric, 1000 ml Class A each Flask, volumetric, 100-mL Class A each Mercuric Sulfate 28 g Pipet, volumetric, 3-mL, Class A each Pipet, volumetric, 10-mL, Class A each Sulfuric Acid, conc 500 ml Wastewater Influent Standard for mixed parameters NH 3 N, NO 3 N, PO 4, COD, SO 4, 500mL TOC Wastewater Effluent Standard, for mixed parameters NH 3 N, NO 3 N, PO 4, COD, SO 4, 500mL TOC Weighing Paper, 76x76 mm 500/pkg Finger cots 2/pkg Gloves, chemical resistant 9-9 ½ 1 1 pair Safety goggles, vented each EZ COD TM Recycling Service with 5-gal 2 bucket mail back 3 each EZ COD TM Recycling Service with 5-gal bucket pick up3 each P 1 Other sizes are available 2 20 and 55 gal are available. ez COD available to U.S. customers only Page 10 of 12

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14 FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: In the U.S.A. Call toll-free Outside the U.S.A. Contact the HACH office or distributor serving you. On the Worldwide Web HACH COMPANY WORLD HEADQUARTERS Telephone: (970) FAX: (970) Hach Company, 2007, All rights reserved. Printed in the U.S.A. Edition 6